1. Field of the Invention
The invention relates to copolymers consisting of monomers containing perfluoroalkyl groups, hydrophilic, ionic and non-ionic monomers and further comonomers. The invention furthermore relates to aqueous dispersions of these fluorine-containing copolymers, to the preparation of the copolymers and their aqueous dispersions and to their use for the oil-, soil- and water-repellant finishing of texthe materials, leather, paper and mineral substrates.
2. Description of the Related Art
It is known from U.S. Pat. Nos. 4,127,711, 4,564,561, 4,366,299 and 4,579,924 that copolymers can be prepared from monomers containing perfluoroalkyl groups, hydrophilic, ionic or non-ionic monomers and, if desired, further comonomers.
The disadvantage is that either the dispersions prepared from these copolymers contain solvents which, upon application, require special safety, precautions due to the relatively low flash point, or the dispersions can only be prepared with the aid of emulsifiers, which, on the other hand, in turn reduce the desired effects, or a very high fluorine content is necessary for ensuring high oil and water repellency, which, on the other hand, leads to harshening of the substrates finished therewith.
Accordingly, the object of the invention is to develop highly effective oil and water repellent finishing agents for texthes, leather, paper and mineral substrates which can be prepared as an aqueous dispersion without using emulsifiers. Rather effective finishing agents for texthes, leather, paper and mineral substrates of the type of fluorine containing copolymers and aqueous dispersions prepared therefrom are known from above cited U.S. Pat. No. 5,247,008.
In detail, these are fluorine-containing copolymers and aqueous dispersions prepared therefrom containing 5 to 50% by weight relative to the total weight of the dispersions, of ingredients other than water (solid content), wherein the copolymers contain copolymerized comonomers in the following percentages by weight, relative to the total weight of the copolymers:
a) 45-75% by weight of (meth)acrylates containing perfluoroalkyl groups, of the formula EQU C.sub.n F.sub.2n+1 --X--OCO--CR.sup.1 .dbd.CH.sub.2 (I)
in which
n represents a number from 4-12, PA1 R.sup.1 denotes hydrogen or methyl and PA1 X represents--(--CH.sub.2 --)m--, --SO.sub.2 --NR.sup.2 --CH.sub.2 --CHR.sup.3 or --O--(--CH.sub.2 --) .sub.m --, where m denotes a number from 1 to 4, R.sup.2 represents C.sub.1 -C.sub.4 -alkyl and R.sup.3 represents hydrogen or methyl, PA1 b) 10 to 50% of monomers of the formulae EQU CH.sub.2 .dbd.CH--CO--OR.sup.4 (IIa) PA1 R.sup.4 represents a C.sub.1 -C.sub.22 -alkyl radical and PA1 R.sup.12 denotes C.sub.2 -C.sub.22 -alkyl PA1 R.sup.7 denotes hydrogen or C.sub.1 -C.sub.8 -alkyl and PA1 p represents a number from 1 to 50, and PA1 R.sup.8 and R.sup.9 independently of one another denote C.sub.1 -C.sub.4 -alkyl and PA1 R.sup.11 represents hydrogen or methyl, PA1 R.sup.10 denotes C.sub.1 -C.sub.4 -alkyl and PA1 Y represents an equivalent of a mono- to tri-valent anion, PA1 X represents --(--CH.sub.2 --).sub.m --, --SO.sub.2 --NR.sup.2 --CH.sub.2 --CHR.sup.3 -- or --O--(--CH.sub.2 --) .sub.m --, m denoting a number from 1 to 4, PA1 R.sup.1, R.sup.3, R.sup.4, R.sup.6, R.sup.7 and R.sup.11 represent, independently of one another, hydrogen or methyl, PA1 R.sup.2, R.sup.9, R.sup.10 and R.sup.12 denote, independently of one another, C.sub.1 -C.sub.4 -alkyl, PA1 R.sup.5 represents a C.sub.1 -C.sub.22 -alkyl, preferably C.sub.1 -C.sub.8 -alkyl, radical, PA1 denotes hydrogen or C.sub.1 -C.sub.8 -alkyl, PA1 p represents a number from 1 to 50, preferably 3 to 25, and PA1 Y represents an equivalent of a mono- to trivalent anion wherefrom the copolymers of U.S. Pat. No. 5,267,008 are disclaimed. PA1 60-90% by weight of component a), PA1 1-35% by weight of component b), PA1 4-25% by weight of component c) and PA1 1-15% by weight of component d), PA1 1-20% by weight of component b), PA1 4-25% by weight of component c) and PA1 1-10% by weight of component d), PA1 &gt;75-90% by weight of component a), PA1 1-&lt;20% by weight of component b) PA1 4-20% by weight of component c) and PA1 1-10% by weight of component d). PA1 &gt;75-85% by weight of component a), PA1 1-18% by weight of component b), PA1 5-15% by weight of component c) and PA1 1-10% by weight of component d). PA1 65-90% by weight of component a), PA1 1-&lt;10% by weight of component b), PA1 4-25% by weight of component c) and PA1 1-10% by weight of component d). PA1 65-85% by weight of component a), PA1 1-&lt;10% by weight of component b), PA1 5-18% by weight of component c) and PA1 1-10% by weight of component d). PA1 Melamine condensation products as described, for example, in DE-A 3,800,845 or in U.S. Pat. No. 2,398,569: PA1 aqueous colloidal suspensions of organosiloxanes disclosed for example, in DE-A 3,307,420: PA1 as paper auxiliaries: agents for retention, wet-fastness and sizing. PA1 a) 10 to 40% by weight of the formula (I), PA1 b) 20 to 95% by weight of the formula (II) and/or styrene, acrylonitrile, vinyl acetate and vinyl propionate, respectively, PA1 c) 4 to 30% by weight of the formula (III), PA1 d) 1 to 15% by weight of the formula (IVa) or (IVb) or (IVc).
and/or EQU CH.sub.2 .dbd.C(CH.sub.3)--CO--OR.sup.12 (IIb)
in which
wherein the monomers (IIa) and/or (IIb) can be completely or partially replaced by one or more monomers of the group consisting of styrene, acrylonitrile, vinyl acetate, vinyl propionate and methyl methacrylate,
c) 4-30% of monomers of the formula ##STR3## in which R.sup.5 and R.sup.6 independently represent hydrogen or methyl and
d) 1 to 15% of monomers of the formula EQU CH.sub.2 .dbd.CR.sup.11 COO--CH.sub.2 CH.sub.2 --N(R.sup.8,R.sup.9)(IVa)
in which
or of monomers of the formula (IVa) in their quaternised form of the formula EQU [CH.sub.2 .dbd.CR.sup.11 --COO--CH.sub.2 CH.sub.2 N(R.sup.8,R.sup.9,R.sup.10)].sup..sym. Y.sup..crclbar. (IVb)
in which additionally
or of monomers of the formula (IVa) in their N-oxidised form of the formula ##STR4## However, it has been found that further effective finishing agents of this type are those, e.g., wherein the comonomer a) is present in approx. 70% by weight, monomer b) in only approx. 8% by weight, and comonomers c) and d) are adjusted accordingly, and those, e.g., wherein the comonomer a) is present in approx. 77% by weight or more, comonomer b) is present in the range of below 10% by weight up to nearly 20% by weight, and comonomers c) and d) are adjusted accordingly.